Catalysis Communications 16 (2011) 56–59

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short Communication

Effect of La2O3 modification on the catalytic performance of Ni/SiC for methanation of

carbon dioxide
Guojuan Zhi a, b, Xiaoning Guo a, b, Yingyong Wang a, Guoqiang Jin a, Xiangyun Guo a,⁎
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Taiyuan 030001, PR China
b
Graduate University of the Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Ni/SiC and La2O3 modified Ni/SiC were prepared by impregnation method and used as the catalysts for
Received 18 July 2011 methanation of CO2. The modified Ni/SiC shows better catalytic activity and stability than pure Ni/SiC. XRD
Received in revised form 30 August 2011 and TPR results indicate that La2O3 can effectively restrain the growth of NiO nanoparticles, improve the dis-
Accepted 30 August 2011
persion of NiO and strengthen the interaction between NiO and SiC. XPS result suggests that La2O3 can change
Available online 10 September 2011
the electron environment surrounding Ni atoms and thus reactant CO2 on the Ni atoms can be activated more
Keywords:
easily.
Ni/SiC catalyst © 2011 Elsevier B.V. All rights reserved.
La2O3 modification
CO2 methanation
Stability

1. Introduction modification on the catalytic performance of Ni/SiC were also

investigated.
Recently, CO2 methanation has attracted considerable attention
since it is an effective method to purify the feed gas for ammonia pro-
2. Experimental
duction and reduce the emission of greenhouse gas CO2 in the atmo-
sphere [1–3]. Numerous supported catalysts of group VIII metals have
2.1. Preparation of Ni/SiC and Ni–La/SiC catalysts
been tested for this reaction. Among these catalytic systems, sup-
ported nickel catalysts are the most widely used materials and have
15 wt.% Ni/SiC was prepared by impregnation method. Firstly,
an excellent activity for CO2 methanation [4]. The catalyst supports
0.4 g of SiC (specific surface area is 50 m 2/g; purchased from Sico-
usually are thermal insulators, such as SiO2, Al2O3, and CeO2 [5–8].
nano, China) was added into Ni(NO3)2·6H2O aqueous solution with
However, CO2 methanation is an exothermic reaction, therefore the
an appropriate concentration under stirring. Then the suspension
accumulative reaction heat make the active phases sintered easily,
was dried at 100 °C and calcined in air at 500 °C for 4 h. La2O3 modi-
which lead to the deactivation of catalysts [9,10]. Therefore, it is nec-
fied Ni/SiC catalyst was prepared by co-impregnation method with
essary to develop new catalysts with high activity and stability for
the same procedure as the Ni/SiC, only the impregnating solution
CO2 methanation.
employed the mixture of Ni(NO3)2·6H2O and La(NO3)3·6H2O. The
It has been established that SiC material is an excellent catalyst
modified catalyst was marked as Ni–La/SiC, in which the content of
support for various reactions because it has admirable chemical inert-
La was 5 wt.%.
ness, thermal conductivity and stability [11,12]. Our previous studies
showed that SiC as a catalyst support had many advantages in high-
temperature or strongly exothermic reactions, such as partial oxida- 2.2. Catalytic performance
tion of methane and methane catalytic combustion [13–15].
La2O3 has been found to be effective for improving the dispersion The catalytic performances of the two catalysts were evaluated in
of active species and thus increasing the activity and stability of the a fixed-bed quartz reactor with an interior diameter of 8 mm at atmo-
catalysts [16,17]. In this work, Ni/SiC and La2O3 modified Ni/SiC cata- spheric pressure. About 200 mg of catalyst was first pretreated at
lysts were prepared for CO2 methanation, and the effects of La2O3 400 °C in 60 ml/min H2 flow for 2 h, and then cooled down to room
temperature in argon. Next, a mixture of H2 and CO2 (molar ratio
about 4.0) was switched to the reactor with a space velocity of
⁎ Corresponding author. Tel./fax: + 86 351 4065282. about 12,000 h − 1. The catalyst was then heated to the reaction tem-
E-mail address: xyguo@sxicc.ac.cn (X. Guo). perature at a rate of 5 °C/min. The composition of the outlet gases was

1566-7367/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.08.037
 G. Zhi et al. / Catalysis Communications 16 (2011) 56–59 57

100
a) b)
100
C Ni-La/SiC
D 90 Ni/SiC

Ni-La/SiC
Ni/SiC A
(%)

80
50

70 B

A B
0
60
150 200 250 300 350 400 0 10 20 30 40 50 60 70
o
Temperature C Time (h)

Fig. 1. Catalytic performances of the catalysts versus temperature (a) and time (b): CO2 conversion of Ni–La/SiC (A) and Ni/SiC (B); CH4 selectivity of Ni–La/SiC (C) and Ni/SiC (D).

analyzed by GC-14B gas chromatograph with TDX-01 column and
TCD detector. The CO2 conversion (XCO2) and CH4 selectivity (SCH4)
were estimated by the following:
XCO2 ¼ ðFCO2 in −FCO2 out Þ=FCO2 in ¼ ðFCH4 out þ FCOout Þ=ðFCH4 out
þ FCOout þ FCO2 out Þ
SCH4 ¼ FCH4 out =ðFCH4 out þ FCOout Þ
2.3. Catalyst characterization
The crystalline phases of the catalysts were characterized by a
Rigaku D-Max/RB X-ray diffractometer (XRD) using Cu Kα radiation
(λ = 1.5418 Å). The morphology and structure of the catalysts were
observed using a JEOL-2100 transmission electron microscope
(TEM). The surface element states were determined by X-ray photo-
electronic spectroscopy (XPS) using Al Kα (hk = 1486.6 eV) X-ray
source. The residual pressure inside the analysis chamber was
below 2 × 10 − 7 Pa. All binding energies were referred to the C (1 s)
line at 284.8 eV.
3. Results and discussion
3.1. Catalytic performance
The activities of Ni/SiC and Ni–La/SiC catalysts for CO2 methana-
tion are shown in Fig. 1. It can be seen that CO2 methanation over
Ni–La/SiC has been ignited at 150 °C, while Ni/SiC only becomes ac-
tive at about 200 °C (Fig. 1a). CO2 conversions of both catalysts have
an obvious increase with the temperature rising. However, CO2 con-
version of Ni–La/SiC is higher than Ni/SiC at the same temperature.
For example, at 250 °C, CO2 conversion and CH4 selectivity of Ni–
ð1Þ La/SiC are 39.6% and 99.6%, respectively; while those of Ni/SiC are
only 3.84% and 88.2%, respectively. At 360 °C, CO2 conversion of
ð2Þ both catalysts can reach their maximum values (~ 85% and 79%).
Above data indicate that Ni–La/SiC has an excellent activity for CO2
methanation. Moreover, Ni–La/SiC catalyst shows a better stability
than Ni/SiC at 360 °C (Fig. 1b), CO2 conversion and CH4 selectivity of
Ni–La/SiC have almost no change during 70 h reaction; while CO2
conversion of Ni/SiC has an obvious decline from 79.0% to 71.1%.
These results suggest that the addition of La2O3 effectively improves
catalytic activity and stability of Ni/SiC.
3.2. XRD characterization
The XRD patterns of fresh Ni/SiC and Ni–La/SiC catalysts are
shown in Fig. 2a. From the patterns, only SiC, NiO phases and a little
of amorphous SiO2 are observed in both catalysts. No La-containing
phase is detected in the modified catalyst probably due to its low con-
tent and high dispersion on catalyst surface [18]. The diffraction peaks
at 2θ = 37.2, 43.3, 62.9, 75.4 and 79.4° can be attributed to NiO [18].
The corresponding peaks in Ni–La/SiC have become broader and
weaker comparing with those in Ni/SiC. The average size of NiO par-
ticles in Ni/SiC is 12.6 nm, which is calculated from the half width of
NiO(111) according to Scherrer–Warren equation [19]. However,

a) b)
Intensity (a.u.)

Intensity (a.u.)

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80

Fig. 2. XRD patterns of fresh (a) and used (b) catalysts.

58 G. Zhi et al. / Catalysis Communications 16 (2011) 56–59
Fig. 3. TEM images of fresh Ni/SiC (a), Ni–La/SiC (b) and used Ni/SiC (c), Ni–La/SiC
(d) catalysts.
the average size of NiO particles is only 8.3 nm in La2O3 modified
Ni/SiC catalyst. This indicates that the highly dispersed La2O3 pro-
motes the dispersion of NiO on the SiC support and thus increases
the active sites on the catalyst surface [20,21]. As a result, the catalytic
activity is greatly enhanced.
Fig. 2b shows the XRD patterns of used catalysts after 70 h. The
diffraction peaks at 2θ = 44.5, 51.8 and 76.4° can be attributed to Ni
[22]. From the Ni (111) plane, the average sizes of Ni particles in
Ni/SiC and Ni–La/SiC are 16.3 nm and 8.0 nm respectively. By com-
paring the particle sizes of fresh and used catalysts, we can find that
the size of Ni particles in Ni–La/SiC does not change significantly.
These suggest that the addition of La2O3 restrains the growth of Ni
particles during the reaction and therefore increases their stability.
3.3. TEM characterization
The TEM images of the fresh and used catalysts are shown in Fig. 3.
From Fig. 3a and b, we can see that the average size of NiO particles in
Intensity (a.u.)
a feedback bond, the stronger the electron-feedback capacity of Ni to
835.95
b activity.
835.33
830 835 840 845
Binding Energy (eV)
Fig. 4. XPS spectra of La 3d5/2 of fresh Ni–La/SiC (a) and used Ni–La/SiC (b) catalysts.
b
a
0 100 200 300 400 500 600 700
Temperature oC
Fig. 5. H2-TPR profiles of Ni/SiC (a) and Ni–La/SiC (b).
Ni–La/SiC is 7.6 nm while it is 14.0 nm in Ni/SiC, indicating that La2O3
as promoter could increase the dispersion of NiO on the support sur-
face. Comparing with the fresh Ni/SiC catalyst, the metallic particles
in the used Ni/SiC have a broader size distribution from 14 to 26 nm
and the average size is 18.8 nm. However, the metallic particles in
the used Ni–La/SiC still keep a narrow size distribution from 5 to
11 nm and the average size is 7.9 nm, which is almost the same as
that in the fresh catalyst. These results well accord with the XRD re-
sults and further confirm that the La2O3 modification can hinder the
migration and aggregation of Ni particles. As a result, the Ni–La/SiC
catalyst shows higher activity and stability.
3.4. XPS characterization
Fig. 4 shows the XPS spectra of La 3d5/2 of fresh and used Ni–La/SiC
catalyst. Because of the overlapping of La 3d3/2 peaks with Ni 2p3/2
peaks, it is difficult to extract reliable Ni 2p3/2 peaks from them
[23,24]. In order to judge whether there are any changes in the sur-
rounding electron environment of Ni atoms, the peak of La 3d5/2 is
studied. In the XPS spectra of fresh Ni–La/SiC catalyst, the peak at
835.95 eV is ascribed to La 3d5/2 [23], and this peak shifts to lower
value at 835.33 eV in the used one. This means that La2O3 was partial-
ly reduced from La2O3 to La2Ox (x b 3) during the prereduction and re-
action of the catalyst. La2Ox as an electron donor may transfer partial
electrons to Ni, resulting in an increase in d-electron density of the
surface Ni atoms [21].
At present, there is a mechanism about CO2 methanation is com-
monly accepted. That is, CO2 is firstly dissociated into CO and then
CO is hydrogenated to CH4 [25–28]. Therefore the dissociation of
adsorbed CO2 on the catalyst is an important step. In Ni–La/SiC cata-
lyst, La2O3 may play dual roles in activating CO2. On the one hand,
the basic La2O3 favors the chemical adsorption and dissociation of
CO2 [29,30]. On the other hand, La2O3 increases d-electron density
of the surface Ni atoms. It is well known that CO2 can be activated
by means of donation of the d-electron of Ni atoms to the vacant
anti-bonding π* orbit of CO2 [26]. The larger the proportion of d\π
adsorb CO2. With the addition of La2O3, the Ni\C bond becomes
stronger and the C\O bond becomes weaker, and thus CO2 can be ac-
tivated more easily. As a result, Ni–La/SiC shows higher catalytic
3.5. TPR analysis
The TPR profiles of Ni/SiC and Ni–La/SiC are shown in Fig. 5. For
Ni/SiC, there is only one reduction peak from 307 °C to 465 °C and
with a center at about 385 °C. This peak can be assigned to the reduc-
tion of NiO, which weakly interacts with the SiC support. For Ni–
 G. Zhi et al. / Catalysis Communications 16 (2011) 56–59
La/SiC, the reduction reaction starts from 302 °C and ends at 550 °C.
The obvious tailing means that the addition of La2O3 has enhanced
the interaction between NiO and SiC. There are three adjacent reduc-
tion peaks at 347 °C, 370 °C and 410 °C, which may indicate different
states of NiO species existing on the catalyst surface. The reduction
peak at lower temperature is generally ascribed to the strong
electron-donor ability of La2O3, which makes NiO easily to be reduced
[21]. The peak at higher temperature (410 °C) may be due to the in-
crease of the polarization effect of the ions in the catalyst surface,
which usually makes the reduction of NiO more difficult [30]. The
above results suggest that La2O3 can strengthen the metal–support
interaction, and therefore inhibit the growth and aggregation of me-
tallic particles during the reduction and reaction processes. These re-
sults further confirm those of catalytic performance and XRD
characterization.
4. Conclusion
La2O3 modified Ni/SiC catalyst was prepared by co-impregnation
method for CO2 methanation. The Ni–La/SiC catalyst exhibits high ac-
tivity and excellent stability, which can stably run at 360 °C over 70 h
with high CH4 selectivity. The excellent catalytic activity of La2O3
modified Ni/SiC results from the smaller Ni particles formed in the
SiC surface, stronger interaction between NiO and SiC, and the more
friendly electron environment for CO2 activation.
Acknowledgments
The work was financially supported by NSFC (Ref. 20973190), the
in-house research project of SKLCC (Ref. SKLCC-2008BWZ010), and
the National Basic Research Program (Ref. 2011CB201405).
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